Yesterday I installed Home Assistant 94.1 on Raspbian / Python 3.7.3. I added the Z-Wave Integration and configured the usb_path and network_key. These were saved in the core.config_entries file.
When I added a secure node from the Z-Wave Network Management section on the Z-Wave Configuration page the node got added but not as a secure node.
After some fiddling around I updated the options.xml file adding the network key to it. After restarting Home Assistant I removed the node and re-added it as a secure node and it worked.
I would have thought that configuring the network key as part of setting up the Z-Wave Integration would allow for secure node setup so I could have been doing something wrong.
I am posting this in case someone sees that I was doing something wrong or runs into the same problem and this fix helps.
digitalhack